Alkylphenol detergents

ABSTRACT

The disclosed technology provides alkylphenol-containing detergent having at least one unit (a) of an alkyl-substituted phenol wherein the alkyl group is derived from oligomers of an olefin compound containing 3 to 8 carbon atoms, wherein the polyolefin-derived alkyl group comprises at least 30 mol percent of an olefin with 4 or more carbon atoms. The invention further relates to a method of lubricating a mechanical device with the lubricant composition.

This application claims priority from U.S. Ser. No. 15/313,128 filed onNov. 22, 2016, now abandoned, which claims priority from PCT ApplicationSerial No.: PCT/US2015/031939 filed on May 21, 2015, which claims thebenefit of U.S. Provisional Application No. 62/003,608 filed on May 28,2014, the entirety of all of which is hereby incorporated by reference.

BACKGROUND OF THE INVENTION

The disclosed technology relates to hydrocarbyl- (e.g. alkyl-) phenoldetergents and their salts. Such compounds and their salts are useful aslubricant additives.

Phenol-based detergents are known. Among these are phenates based onphenolic monomers, linked with sulfur bridges or alkylene bridges suchas methylene linkages derived from formaldehyde. The phenolic monomersthemselves are typically substituted with an aliphatic hydrocarbyl groupto provide a measure of oil solubility. The hydrocarbyl groups may bealkyl groups, and, historically, dodecylphenol (or propylenetetramer-substituted phenol) has been widely used. An early reference tobasic sulfurized polyvalent metal phenates is U.S. Pat. No. 2,680,96,Walker et al., Jun. 1, 1954; see also U.S. Pat. No. 3,372,116,Meinhardt, Mar. 6, 1968.

Recently, however, certain alkylphenols and products prepared from themhave come under increased scrutiny due to their association as potentialendocrine disruptive materials. In particular, alkylphenol detergentswhich are based on phenols alkylated with oligomers of propylene,specifically propylene teramer (or tetrapropenyl), may contain residualalkyl phenol species. There is interest, therefore, in developingalkyl-substituted phenol detergents, for uses in lubricants, fuels, andas industrial additives, which contain a reduced or eliminated amount ofdodecylphenol component and other substituted phenols having propyleneoligomer substituents of 10 to 15 carbon atoms. Nevertheless, it isdesirable that the products should have similar oil-solubilityparameters as phenates prepared from C10-15 propylene oligomers.

There have been several efforts to prepare phenate detergents that donot contain Cn alkyl phenols derived from oligomers of propylene. U.S.Pat. No. 7,435,709, Stonebraker et al., Oct. 14, 2008, discloses alinear alkylphenol derived detergent substantially free of endocrinedisruptive chemicals. It comprises a salt of a reaction product of (1)an olefin having at least 10 carbon atoms, where greater than 90 mole %of the olefin is a linear C20-C30 n-alpha olefin, and wherein less than10 mole % of the olefin is a linear olefin of less than 20 carbon atoms,and less than 5 mole % of the olefin a branched chain olefin of 18carbons or less, and (2) a hydroxyaromatic compound.

U.S. Application 2011/0190185, Sinquin et al, Aug. 4, 2011, discloses anoverbased salt of an oligomerized alkylhydroxyaromatic compound. Thealkyl group is derived from an olefin mixture comprising propyleneoligomers having an initial boiling point of at least about 195° C. anda final boiling point of greater than 325° C. The propylene oligomersmay contain a distribution of carbon atoms that comprise at least about50 weight percent of C14 to C20 carbon atoms.

U.S. Application 2011/0124539, Sinquin et al, May 26, 2011, discloses anoverbased, sulfurized salt of an alkylated hydroxyaromatic compound. Thealkyl substituent is a residue of at least one isomerized olefin havingfrom 15 to about 99 wt. % branching. The hydroxyaromatic compound may bephenol, cresols, xylenols, or mixtures thereof.

U.S. Application 2011/0118160, Campbell et al., May 19, 2011, disclosesan alkylated hydroxyaromatic compound substantially free of endocrinedisruptive chemicals. An alkylated hydroxyaromatic compound is preparedby reacting a hydroxyaromatic compound with at least one branchedolefinic propylene oligomer having from about 20 to about 80 carbonatoms. Suitable hydroxyaromatic compounds include phenol, catechol,resorcinol, hydroquinone, pyrogallol, cresol, and the like.

U.S. Application 2010/0029527, Campbell et al., Feb. 4, 2010, disclosesan overbased salt of an oligomerized alkylhydroxyaromatic compound. Thealkyl group is derived from an olefin mixture comprising propyleneoligomers having an initial boing point of at least about 195° C. and afinal boiling point of no more than about 325° C. Suitablehydroxyaromatic compounds include phenol, catechol, resorcinol,hydroquinone, pyrogallol, cresol, and the like.

U.S. Application 2008/0269351, Campbell et al., Oct. 30, 2008, disclosesan alkylated hydroxyaromatic compound substantially free of endocrinedisruptive chemicals, prepared by reacting a hydroxyaromatic compoundwith a branched olefinic oligomer having from about 20 to about 80carbon atoms.

WO/PCT application 2013/059173, Cook et al., discloses an overbased saltof an oligomerized alkylhydroxyaromatic compound. The alkyl group is acombination of very short hydrocarbyl group (i.e. 1 to 8 carbon atoms)and a long hydrocarbyl group (at least about 25 carbon atoms). Suitablecompounds include those made from a mixture of para-cresol andpolyisobutylene-substituted phenol.

Other general technology includes that of U.S. Pat. No. 6,310,009,Carrick et al., Oct. 30, 2001, which discloses salts of the generalstructure

where R may be an alkyl group of 1 to 60 carbon atoms, e.g., 9 to 18carbon atoms. It is understood that R¹ will normally comprise a mixtureof various chain lengths, so that the foregoing numbers will normallyrepresent an average number of carbon atoms in the R¹ groups (numberaverage).

SUMMARY OF THE INVENTION

The disclosed technology, may solve at least one problem of providing aphenolic material with appropriate oil solubility, providing anti-wearperformance, providing oxidation performance, viscosity performance, anddetergency (characteristic of moderate chain length alkyl groups). Inone embodiment the disclosed technology may also solve the problem ofcontaining C12 alkyl phenol moieties i.e., the disclosed technology maybe free from or substantially free from C12 alkyl phenol moietiestypically formed from oligomerisation or polymerisation of propylene.

The disclosed technology provides an alkylphenol-containing detergentcompound comprising an alkyl-substituted phenol wherein the alkyl groupis derived from oligomers of an olefin compound containing 3 to 8 carbonatoms, and wherein the polyolefin-derived alkyl group comprises at least30 mol percent of an olefin with 4 or more carbon atoms. The alkylphenolcompound may be derived from oligomers of n-butene, where the alkylgroup is a hydrocarbyl group of 12 to 48 carbon atoms. In certainembodiments, the alkylphenol detergent is substantially free of (orentirely free of, or contains less than 5 percent or 3 percent or 1percent or 0.3 percent or 0.1 percent by mole of) oligomer unitscontaining propylene. In certain embodiments, the alkylphenol detergentis substantially free from or substantially free from C12 alkyl phenolmoieties.

The alkylphenol-containing detergent may be a sulfur-bridged phenatedetergent, a sulfur-free alkylene-bridged phenate detergent, asalicylate detergent, or mixtures thereof. Detergents of this type areionic detergents, i.e. they generally comprise a salt of the detergentsubstrate (the phenol-containing material) and a suitable cationiccounterion. Detergents of the disclosed technology may bemetal-containing salts, amine or ammonium containing salts, or mixturesthereof. In one embodiment, the detergent comprises one or more alkalimetals, one or more alkaline earth metals, or mixtures thereof.

In another expression, the disclosed technology provides a bridgeddimeric or oligomeric phenolic compound comprising an oligomericmaterial comprising: at least one monomer unit of an alkyl-substitutedphenol wherein the alkyl group may be derived from oligomers of anolefin compound containing 3 to 8 carbon atoms, or mixtures thereof; andat least one sulfur-containing or carbon-containing bridging group; or asalt of said oligomeric material; wherein the alkyl group may be ahydrocarbyl group of 12 to 50 carbon (16 to 40, or 16 to 36 or 18 to 28or 18 to 36).

The disclosed technology may include a process to prepare analkylphenol-containing detergent compound comprising (i) forming analkyl-substituted phenol wherein the alkyl group is derived fromoligomers of an olefin compound containing 3 to 8 carbon atoms, andwherein the polyolefin-derived alkyl group comprises at least 30 molpercent of an olefin with 4 or more carbon atoms to form a substrate,and then reacting the substrate with a metal base (such as an alkalimetal or alkaline earth metal oxide or hydroxide), in the presence ofcarbon dioxide to form an alkylphenol-containing detergent. The reactionconditions for the process are known in the art and include alkylationof phenol in the presence of known catalysts including BF₃, AlCl₃, orHF. The reaction of the substrate with a metal base), in the presence ofcarbon dioxide are well known processes in the art of preparingdetergents.

The disclosed technology also provides a lubricant comprising an oil oflubricating viscosity and said alkylphenol detergent, as well as amethod of lubricating a mechanical device with said lubricant.

The disclosed technology also provides a method of lubricating amechanical device comprising supplying to the mechanical device alubricating composition disclosed herein.

The disclosed technology also provides for the use of the alkylphenoldetergent in a lubricating composition to provide detergency, depositcontrol and oxidative stability to the lubricant.

DETAILED DESCRIPTION OF THE INVENTION

The disclosed technology provides an alkylphenol detergent, alubricating composition, a method for lubricating an internal combustionengine and a use as disclosed herein.

One of the materials of the presently disclosed technology may be abridged alkylphenol compound. Such materials in general, their methodsof preparation, and use in lubricants are well known from, for instance,the above-referenced U.S. Pat. No. 2,680,096, Walker et al. They may beprepared starting from alkyl phenol such as alkylphenols derived fromoligomers of n-butene, or mixtures thereof, any of which are readilyavailable as starting materials. The alkylation of phenol and itshomologues is well known, typically by catalyzed reaction of an olefin,often an □-olefin, with phenol (or with salicylic acid or anotherhomologue, as the case may be). Alkylation of phenol is described ingreater detail in the Kirk-Othmer Encyclopedia of Chemical Technology,third edition (1978) vol. 2, pages 82-86, John Wiley and Sons, New York.

Linking of alkyl (or more generally, hydrocarbyl) phenols to formoligomeric species, is also well known. They may be condensed, forinstance, with formaldehyde or with other aldehydes or ketones such asacetone to form methylene (or alkylene) bridged structures, as describedon pages 76-77 of the above cited Kirk-Othmer reference. If condensationwith an aldehyde or ketone is intended, it is desirable that thealdehyde or ketone not be a C12 species, to avoid the formation of anyC12 substituted phenolic materials. In certain embodiments the materialmay be an aldehyde of 8 or fewer carbon atoms, such as 1 to 4, or 1 or2, or a single carbon atom (formaldehyde). The length of the resultingoligomeric chain of phenolic and alkylene units will depend to someextent on the molar ratio of the reactants, as is well known. Thus anequimolar amount of phenol and formaldehyde provides a condensate with arelatively longer oligomeric chain than that obtained when there is astoichiometric excess of one species or the other. Under certainconditions, carbon- and oxygen-containing linkages may also be formed,such as those of the general structure —CH₂—O—CH₂— or homologues inwhich the hydrogens are replaced by alkyl groups. These may be formed bythe condensation of more than a single aldehyde or ketone group. Suchstructures are known, for example, from U.S. Pat. No. 6,310,009, seecol. 2 lines 14-17 and col. 6 lines 1-45. Thus the linking groupsprepared form aldehydes or ketones may be generally described as“carbon-containing” bridging groups, e.g., an alkylene bridge or anether bridge.

Substituted phenols may also be linked together to make sulfur bridgedspecies, which may include bridges of single sulfur atoms (—S—) ormultiple sulfur atoms (e.g., —S_(x)— where x may be 2 to 8, typically 2or 3). Sulfurized phenols may be prepared by reaction with active sulfurspecies such as sulfur monochloride or sulfur dichloride as described onpages 79-80 of the Kirk-Othmer reference or with elemental sulfur, asdescribed, for instance, in U.S. Pat. No. 2,680,096. Sulfurization (withsulfur) may be conducted in the presence of a basic metal compound suchas calcium hydroxide or calcium oxide, thus preparing a metal salt, asdescribed in greater detail, below. Basic sulfurized phenates and amethod for their preparation are also disclosed in U.S. Pat. No.3,410,798, Cohen, Nov. 12, 1968. The examples and claim 1 thereofdisclose a method, comprising reacting at a temperature above about 150°C., (A) a phenol, (B) sulfur, and (C) an alkaline earth base, in thepresence of a promoter comprising (D) about 5-20 mole percent, based onthe amount of component A, of a carboxylic acid or alkali metal,alkaline earth metal, zinc, or lead salt thereof and (E) as a solvent, acompound of the formula R(OR′)_(X)OH, e.g., a polyalkylene glycol. Thephenol (A), in turn, may be a hydrocarbyl-substituted phenol which maybe prepared by mixing a hydrocarbon and a phenol at a temperature ofabout 50-200° C. in the presence of a suitable catalyst such as aluminumtrichloride (col. 2 line 51 of U.S. Pat. No. 3,410,798, and followingtext).

Alkylphenol

In the present technology, the alkyl group is derived from a polyolefincompound comprising n-butene (also referred to as 1-butene) monomers,higher alpha-olefins, or mixtures thereof. In addition to n-butene,suitable alpha-olefins include isobutylene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1-nonene, 1-decene, and mixtures thereof. In oneembodiment, the alkyl group of the alkylphenol is a polyolefin compoundcomprising at least 25 mol % 1-butene, at least 50 mol % 1-butene, or atleast 75 mol % 1-butene. In one embodiment, the alkyl group of thealkylphenol consists of oligomers or polymers of 1-butene.

Suitable polyolefins include oligomers or polymers of n-butene. A butenepolymer or oligomer containing 8 to 48 carbon atoms would contain 2 to12 butene monomer units. An n-butene polymer or oligomer containing 12to 32 carbon atoms would contain 3 or 8 n-butene monomer units. Furtherdetails of alkylation are disclosed in the above-cited Kirk Othmerreference.

The alkylphenol from which the detergent may be derived may becharacterized as a phenol substituted with one or more alkyl groupsderived from a polyolefin or oligomerized olefin as described above. Thealkylphenol may contain one or more alkyl groups derived from anoligomer (or polymer) of n-butene. In one embodiment, the alkylphenolmay be C₈ to C₄₈ alkylphenol, a C₁₂ to C₃₂ alkylphenol, a C₁₆ to C₂₄alkylphenol, or mixtures thereof, wherein the alkyl groups are oligomersof n-butene.

Bridged Phenol Detergents

In certain embodiments, the alkylphenol-containing detergent may be asulfur-bridged phenate detergent, a sulfur-free alkylene-bridged phenatedetergent, or mixtures thereof. Detergents of this type are ionic(usually metal) salts of bridged phenolic compounds. The bridgedphenolic compound material may be represented by the structure

-   -   or more generally

or isomers thereof, wherein each R may be an aliphatic hydrocarbyl groupderived from oligomers of n-butene, higher alphaolefins, or mixturesthereof, and wherein the hydrocarbyl group contains 8 to 48 carbonatoms. The average number of carbon atoms in all the R groups, combined,may be 16 to 100 (or 20 to 50, or 24 to 36 or 14 to 20 or 18 to 36).Where the bridging group may be listed as “X”, each X may independentlya carbon-containing bridge, or an alkylene group, or a methylene group,or a bridge of 1 or more sulfur atoms represented by S_(y), where y maybe 1 to 4, especially 1 or 2. In these structures, n may, in certainembodiments, be 0 to 8, or 1 to 6, or 1 to 4, or 2 to 4. That is, thebridged material may, in these embodiments, contain 2 to 10 bridgedphenolic groups, or 3 to 7, or 3 to 5, or 4 such groups. Since n may bezero, it may be evident that throughout this specification, theexpression “oligomeric” may be interpreted to include dimeric species.Accordingly, sometimes the expression “dimeric or oligomeric” may beused to express this concept, which may include, as above, as anexample, 0 to 8 interior units bracketed by [ ]_(n) or 2 to 10 unitsoverall. In certain embodiments, in the above structure, one or two ofthe R groups are aliphatic hydrocarbyl groups containing 30 to 200 or 35to 80 carbon atoms and the remainder of the R groups are methyl groups.

In one embodiment, the sulfur-bridged alkylphenol-containing detergentmay be an oligomer of p-(tetrabutenyl)phenol. A sulfur-bridged oligomerof oligobutenylphenol may be represented by the structure (III)

where n=0 to 4, and m=1 to 3.

In certain embodiments, the alkylene-bridged phenate detergent may be asaligenin detergent. A saligenin detergent contains a bridged-alkylphenol compound that may be an alkylene coupled alkylphenol representedby the structure (IV)

where each R may be an aliphatic hydrocarbyl group derived fromoligomers of n-butene, higher alphaolefins, or mixtures thereof, andwherein the hydrocarbyl group contains 8 to 48 carbon atoms; where theeach bridging group (X) may be independently a carbon-containing bridge,or a hydrocarbylether linkage (such as —CH₂—O—CH₂—), or an alkylenegroup, or a methylene group; each Y may be independently —CHO or —CH₂OH;wherein the —CHO groups comprise at least about 10 mole percent of the Xand Y groups; and n may be an integer from 1 to 10.

In certain embodiments, the alkylene-bridged phenate detergent may be asalixarate detergent. A salixarate detergent contains a bridged-alkylphenol compound that may be an alkylene coupled alkylphenol that may befurther bridged or coupled to salicylic acid. The bridged phenol of asalixarate may be represented by the structure (V)

where R may be an aliphatic hydrocarbyl group derived from oligomers ofn-butene, higher alphaolefins, or mixtures thereof, and wherein thehydrocarbyl group contains 8 to 48 carbon atoms; where the each bridginggroup (X) may be independently a carbon-containing bridge, or analkylene group, or a methylene group; and n may be an integer from 1 to10

The bridged alkylphenol detergents may be neutral or overbased orsuperbased. Such overbased detergents are generally single phase,homogeneous Newtonian systems characterized by a metal and/or ammoniumcontent in excess of that which would be present for neutralizationaccording to the stoichiometry of the metal or ammonium and theparticular acidic organic compound reacted with the metal or ammoniumcompound. The overbased materials are typically prepared by reacting anacidic material (typically an inorganic acid or lower carboxylic acidsuch as carbon dioxide) with a mixture of bridged alkylphenol compounds(referred to as a substrate), a stoichiometric excess of a metal base,typically in a reaction medium of an one inert, organic solvent (e.g.,mineral oil, naphtha, toluene, xylene) for the acidic organic substrate.Typically also a small amount of promoter such as a phenol or alcohol ispresent, and in some cases a small amount of water. The acidic organicsubstrate will normally have a sufficient number of carbon atoms toprovide a degree of solubility in oil.

In certain embodiments, the overbased bridged-phenol detergent may be ametal-containing detergent, an amine or ammonium containing detergent,or mixtures thereof. In one embodiment the overbased metal-containingdetergent may be zinc, sodium, calcium or magnesium salts of a phenate,sulfur containing phenate, salixarate or saligenin. In one embodiment,the overbased detergent comprises a salt of an alkylamine or quaternaryammonium compound. Overbased salixarates, phenates and saligeninstypically have a total base number (TBN) (by ASTM D3896) of 120 to 600mg KOH/g.

Salicylates

In certain embodiments, the alkylphenol-containing detergent may be analkylsalicylate or salicylate detergent. A salicylate detergent may be aneutral or overbased metal salt of alkylsalicylic acid. Alkylsalicylicacid may be represented by the formula (VI)

where R may be an aliphatic hydrocarbyl group derived from oligomers ofn-butene, higher alphaolefins, or mixtures thereof, and wherein thehydrocarbyl group contains 8 to 48 carbon atoms.

The alkylsalicylate may be a neutral or nearly neutral salt ofalkylsalicylic acid; by nearly neutral, it is meant that there is anexcess of base of no more than 15 mol percent, i.e. if the salt ismetal-containing, the metal ratio is 1.15 or less. In one embodiment theneutral salt of the alkylsalicylic acid may be an amine or ammoniumsalt, a metal salt, or mixtures thereof.

Amines suitable for use in the preparation of the neutral amine saltedalkylsalicylate are not overly limited and may include any alkyl amine,though generally are fatty acid amines derived from fatty carboxylicacids. The alkyl group present in the amine may contain from 10 to 30carbon atoms, or from 12 to 18 carbon atoms, and may be linear orbranched. In some embodiments the alkyl group may be linear andunsaturated. Typical amines include pentadecylamine, octadecylamine,cetylamine, oleylamine, decylamine, dodecylamine, dimethyldodecylamine,tridecylamine, heptadecylamine, octadecylamine, stearylamine, and anycombination thereof. In some embodiments the fatty acid derived aminesalt of an alkylsalicylic acid may be a salt of oleylamine. In certainembodiments, the amine may be a gamma-aminoester compound; aminoestersof this type may be derived from Michael addition of a primary amine toan alkyl diester of itaconic acid represented by the formula

where R¹ and R² are hydrocarbyl groups containing 2 to 30 carbon atoms,and R³ is a hydrocarbyl group containing 4 to 50 carbon atoms. In someembodiments, R³ of the aminoester compound is an alkyl group that has atleast one hydrocarbyl group substituted at the 1-, or 2-position of thealkyl group. In one embodiment, the aminoester is dibutyl2-(((2-ethylhexyl)-amino)methyl)succinate.

In certain embodiments, the neutral salt of the alkylsalicylic acid maybe a quaternary ammonium salt, also referred to as a quaternary nitrogencompound. Quaternary nitrogen compounds are characterized in that thenitrogen atom is four-coordinate; this results in a cationic speciesthat is not protic, i.e. an acidic proton is not released under basicconditions. Quaternary nitrogen compounds may be characterized asfalling into two large groups, four coordinate tetrahydrocarbylammoniumcompounds, for example tetrabutylammonium, and three coordinate aromaticcompounds, for example N-hydrocarbylpyridinium.

In some embodiments the quaternary nitrogen salt may comprise thereaction product of (a) hydrocarbyl-substituted compound having atertiary amino group and (b) a quaternizing agent suitable forconverting the tertiary amino group of (a) to a quaternary nitrogen,wherein the quaternizing agent may be chosen from dialkyl sulfates,benzyl halides, hydrocarbyl substituted carbonates; hydrocarbyl epoxidesin combination with an acid or mixtures thereof. In one embodiment, thequaternary nitrogen salt comprises the reaction product of (i) at leastone compound chosen from: a polyalkene-substituted amine having at leastone tertiary amino group and/or a Mannich reaction product having atertiary amino group; and (ii) a quaternizing agent.

The alkylphenol-containing detergents, be they phenates, saligenins,salixrates, or salicylates, may be metal-containing detergents.Metal-containing detergents may be neutral, or very nearly neutral, oroverbased. An overbased detergent contains a stoichiometric excess of ametal base for the acidic organic substrate. This is also referred to asmetal ratio. The term “metal ratio” is the ratio of the totalequivalents of the metal to the equivalents of the acidic organiccompound. A neutral metal salt has a metal ratio of one. A salt having4.5 times as much metal as present in a normal salt will have metalexcess of 3.5 equivalents, or a ratio of 4.5. The term “metal ratio” isalso explained in standard textbook entitled “Chemistry and Technologyof Lubricants”, Third Edition, Edited by R. M. Mortier and S. T.Orszulik, Copyright 2010, page 219, sub-heading 7.25.

In one embodiment the overbased metal-containing alkylphenol detergentmay be calcium or magnesium overbased detergent. In one embodiment, theoverbased detergent may comprise a calcium alkylphenol detergent with ametal ratio of at least 1.5, at least 3, at least 5, or at least 7. Incertain embodiments, the overbased calcium alkylphenol detergent mayhave a metal ratio of 1.5 to 25, 2.5 to 20 or 5 to 16.

Alternatively, the alkylphenol detergent may be described as having TBN.Overbased phenates and salicylates typically have a total base number of120 to 600 mg KOH/g, or 150 to 550 mg KOH/g, or 180 to 350 mg KOH/g. Theamount of the alkylphenol-containing detergent present in a lubricantcomposition may be defined as the amount necessary to deliver an amount,or range of amounts, of TBN to the lubricant composition. In certainembodiments, the alkylphenol-containing detergent may be present in alubricant composition in amount to deliver 0.5 to 10 TBN to thecomposition, or 1 to 7 TBN, or 1.5 to 5 TBN to the composition.

Overbased detergents may also be defined as the ratio of the neutraldetergent salt, also referred to as detergent soap, and the detergentash. The overbased detergent may have a weight ratio of ash to soap of3:1 to 1:8, or 1.5:1 to 1 to 4.1, or 1.3:1 to 1:3.4.

The product of the disclosed technology may beneficially be used as anadditive in a lubricant. The amount of the alkylphenol detergent in alubricant may be 0.1 to 8 percent by weight, on an oil-free basis, butincluding the calcium carbonate and other salts present in an overbasedcomposition. When present as an overbased detergent, the amount maytypically be in the range of 0.1 to 25 weight percent, or 0.2 to 28, or0.3 to 20, or 0.5 to 15 percent. The higher amounts are typical ofmarine diesel cylinder lubricants, e.g., 1 or 3 or 5 percent up to 25,20, or 15 percent. Amounts used in gasoline or heavy-duty diesel engines(not marine) will typically be in lower ranges, such as 0.1 to 10percent or 0.5 to 5 or 1 to 3 percent by weight. When used as asubstantially neutral or non-overbased salt, its amount may typically becorrespondingly less for each of the engine types, e.g., 0.1 to 10percent or 0.2 to 8 or 0.3 to 6 percent.

In certain embodiments, the amount of the alkylphenol detergent in alubricant may be measured as the amount of alkylphenol-containing soapthat is provided to the lubricant composition, irrespective of anyoverbasing. In one embodiment, the lubricant composition may contain0.05 weight percent to 1.5 weight percent alkylphenol-containing soap,or 0.1 weight percent to 0.9 weight percent alkylphenol-containing soap.In one embodiment, the alkylphenol-containing soap provides 20 percentby weight to 100 percent by weight of the total detergent soap in thelubricating composition. In one embodiment the alkylphenol-containingsoap provides 30 percent by weight to 80 percent by weight of the totaldetergent soap, or 40 percent by weight to 75 percent by weight of thetotal detergent soap of the lubricating composition.

A lubricant composition may contain alkylphenol-containing detergentsdifferent from that of the disclosed technology. In one embodiment, thelubricant composition of the disclosed technology comprises thealkylphenol detergent of the disclosed technology in an amount 0.1 to 25weight percent, or 0.2 to 28, or 0.3 to 20, or 0.5 to 15 weight percent,and is free of or substantially free of an alkylphenol-containingdetergent derived from alkylphenol which is derived from oligomers ofpropylene, especially tetrapropenyl. “Substantially free of” in thiscase means no more than 0.01 weight percent or an amount considered toarise through contamination or other unintentional means.

Oil of Lubricating Viscosity

The lubricating composition comprises an oil of lubricating viscosity.Such oils include natural and synthetic oils, oil derived fromhydrocracking, hydrogenation, and hydrofinishing, unrefined, refined,re-refined oils or mixtures thereof. A more detailed description ofunrefined, refined and re-refined oils is provided in InternationalPublication WO2008/147704, paragraphs [0054] to [0056] (a similardisclosure is provided in US Patent Application 2010/197536, see [0072]to [0073]). A more detailed description of natural and syntheticlubricating oils is described in paragraphs [0058] to [0059]respectively of WO2008/147704 (a similar disclosure is provided in USPatent Application 2010/197536, see [0075] to [0076]). Synthetic oilsmay also be produced by Fischer-Tropsch reactions and typically may behydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodimentoils may be prepared by a Fischer-Tropsch gas-to-liquid syntheticprocedure as well as other gas-to-liquid oils.

Oils of lubricating viscosity may also be defined as specified in April2008 version of “Appendix E—API Base Oil Interchangeability Guidelinesfor Passenger Car Motor Oils and Diesel Engine Oils”, section 1.3Sub-heading 1.3. “Base Stock Categories”. The API Guidelines are alsosummarized in U.S. Pat. No. 7,285,516 (see column 11, line 64 to column12, line 10).

In one embodiment the oil of lubricating viscosity may be an API Group Ito III mineral oil, a Group IV synthetic oil, or a Group V naphthenic orester synthetic oil, or mixtures thereof. In one embodiment the oil oflubricating viscosity may be an API Group II, Group III mineral oil, ora Group IV synthetic oil, or mixtures thereof.

The amount of the oil of lubricating viscosity present is typically thebalance remaining after subtracting from 100 weight % the sum of theamount of the additives of the disclosed technology and the otherperformance additives.

The lubricating composition may be in the form of a concentrate and/or afully formulated lubricant. If the lubricating composition of thedisclosed technology (comprising the additives disclosed herein) is inthe form of a concentrate which may be combined with additional oil toform, in whole or in part, a finished lubricant), the ratio of the ofthese additives to the oil of lubricating viscosity and/or to diluentoil include the ranges of 1:99 to 99:1 by weight, or 80:20 to 10:90 byweight. Typically the lubricating composition of the disclosedtechnology comprises at least 50 weight %, or at least 60 weight %, orat least 70 weight %, or at least 80 weight % of an oil of lubricatingviscosity.

Other Performance Additives

A lubricating composition may be prepared by adding the product of theprocess described herein to an oil of lubricating viscosity, optionallyin the presence of other performance additives (as described hereinbelow).

The lubricating composition of the disclosed technology optionallycomprises other performance additives. The other performance additivesinclude at least one of metal deactivators, viscosity modifiers (otherthan the soot dispersing additive of the present invention), detergents,friction modifiers, antiwear agents, corrosion inhibitors, dispersants(other than those of the present invention), extreme pressure agents,antioxidants, foam inhibitors, demulsifiers, pour point depressants,seal swelling agents and mixtures thereof. Typically, fully-formulatedlubricating oil will contain one or more of these performance additives.

In one embodiment the invention provides a lubricating compositionfurther comprising an overbased metal-containing detergent in additionto the alkylphenol-containing detergent of the present invention. Themetal of the metal-containing detergent may be zinc, sodium, calcium,barium, or magnesium. Typically the metal of the metal-containingdetergent may be sodium, calcium, or magnesium.

The overbased metal-containing detergent may be chosen from sulfonates,non-sulfur containing phenates, sulfur containing phenates, salixarates,salicylates, and mixtures thereof, or borated equivalents thereof. Theoverbased detergent may be borated with a borating agent such as boricacid.

The overbased metal-containing detergent may also include “hybrid”detergents formed with mixed surfactant systems including phenate and/orsulfonate components, e.g. phenate/salicylates, sulfonate/phenates,sulfonate/salicylates, sulfonates/phenates/salicylates, as described;for example, in U.S. Pat. Nos. 6,429,178; 6,429,179; 6,153,565; and6,281,179. Where, for example, a “hybrid” sulfonate/phenate detergent isemployed, the “hybrid” detergent would be considered equivalent toamounts of distinct phenate and sulfonate detergents introducing likeamounts of phenate and sulfonate soaps, respectively.

Typically, an overbased metal-containing detergent may be a zinc,sodium, calcium or magnesium salt of a sulfonate, a phenate, sulfurcontaining phenate, salixarate or salicylate. Overbased sulfonates,salixarates, phenates and salicylates typically have a total base numberof 120 to 700 TBN.

Typically, the overbased metal-containing detergent may be a calcium ormagnesium an overbased detergent.

In another embodiment the lubricating composition further comprises acalcium sulfonate overbased detergent having a TBN of 120 to 700. Theoverbased sulfonate detergent may have a metal ratio of 12 to less than20, or 12 to 18, or 20 to 30, or 22 to 25.

Overbased sulfonates typically have a total base number of 120 to 700,or 250 to 600, or 300 to 500 (on an oil free basis). Overbaseddetergents are known in the art. In one embodiment the sulfonatedetergent may be a predominantly linear alkylbenzene sulfonate detergenthaving a metal ratio of at least 8 as is described in paragraphs [0026]to [0037] of US Patent Application 2005065045 (and granted as U.S. Pat.No. 7,407,919). Linear alkyl benzenes may have the benzene ring attachedanywhere on the linear chain, usually at the 2, 3, or 4 position, ormixtures thereof. The predominantly linear alkylbenzene sulfonatedetergent may be particularly useful for assisting in improving fueleconomy. In one embodiment the sulfonate detergent may be a metal saltof one or more oil-soluble alkyl toluene sulfonate compounds asdisclosed in paragraphs [0046] to [0053] of US Patent Application2008/0119378.

In one embodiment the lubricating composition further comprises 0.01 wt% to 2 wt %, or 0.1 to 1 wt % of a detergent different from thealkylphenol detergent of the disclosed technology, wherein the furtherdetergent is chosen from sulfonates, non-sulfur containing phenates,sulfur containing phenates, sulfonates, salixarates, salicylates, andmixtures thereof, or borated equivalents thereof.

In one embodiment the lubricating composition further comprises a“hybrid” detergent formed with mixed surfactant systems includingphenate and/or sulfonate components, e.g. phenate/salicylates,sulfonate/phenates, sulfonate/salicylates, orsulfonates/phenates/salicylates.

The lubricating composition in a further embodiment comprises anantioxidant, wherein the antioxidant comprises a phenolic or an aminicantioxidant or mixtures thereof. The antioxidants include diarylamines,alkylated diarylamines, hindered phenols, or mixtures thereof. Whenpresent the antioxidant is present at 0.1 wt % to 3 wt %, or 0.5 wt % to2.75 wt %, or 1 wt % to 2.5 wt % of the lubricating composition.

The diarylamine or alkylated diarylamine may be a phenyl-α-naphthylamine(PANA), an alkylated diphenylamine, or an alkylated phenylnapthylamine,or mixtures thereof. The alkylated diphenylamine may includedi-nonylated diphenylamine, nonyl diphenylamine, octyl diphenylamine,di-octylated diphenylamine, di-decylated diphenylamine, decyldiphenylamine and mixtures thereof. In one embodiment the diphenylaminemay include nonyl diphenylamine, dinonyl diphenylamine, octyldiphenylamine, dioctyl diphenylamine, or mixtures thereof. In anotherembodiment the alkylated diphenylamine may include nonyl diphenylamine,or dinonyl diphenylamine. The alkylated diarylamine may include octyl,di-octyl, nonyl, di-nonyl, decyl or di-decyl phenylnapthylamines.

The hindered phenol antioxidant often contains a secondary butyl and/ora tertiary butyl group as a sterically hindering group. The phenol groupmay be further substituted with a hydrocarbyl group (typically linear orbranched alkyl) and/or a bridging group linking to a second aromaticgroup. Examples of suitable hindered phenol antioxidants include2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol,4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butyl¬phenol or4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butyl¬phenol.In one embodiment the hindered phenol antioxidant may be an ester andmay include, e.g., Irganox™ L-135 from Ciba. A more detailed descriptionof suitable ester-containing hindered phenol antioxidant chemistry isfound in U.S. Pat. No. 6,559,105.

The lubricating composition may in a further embodiment include adispersant, or mixtures thereof. The dispersant may be a succinimidedispersant, a Mannich dispersant, a succinamide dispersant, a polyolefinsuccinic acid ester, amide, or ester-amide, or mixtures thereof. In oneembodiment the dispersant may be present as a single dispersant. In oneembodiment the dispersant may be present as a mixture of two or threedifferent dispersants, wherein at least one may be a succinimidedispersant.

The succinimide dispersant may be derived from an aliphatic polyamine,or mixtures thereof. The aliphatic polyamine may be aliphatic polyaminesuch as an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine,or mixtures thereof. In one embodiment the aliphatic polyamine may beethylenepolyamine. In one embodiment the aliphatic polyamine may bechosen from ethylenediamine, diethylenetriamine, triethylenetetramine,tetra¬ethylene¬pentamine, pentaethylene-hexamine, polyamine stillbottoms, and mixtures thereof.

In one embodiment the dispersant may be a polyolefin succinic acidester, amide, or ester-amide. For instance, a polyolefin succinic acidester may be a polyisobutylene succinic acid ester of pentaerythritol,or mixtures thereof. A polyolefin succinic acid ester-amide may be apolyisobutylene succinic acid reacted with an alcohol (such aspentaerythritol) and a polyamine as described above.

The dispersant may be an N-substituted long chain alkenyl succinimide.An example of an N substituted long chain alkenyl succinimide ispolyisobutylene succinimide. Typically the polyisobutylene from whichpolyisobutylene succinic anhydride is derived has a number averagemolecular weight of 350 to 5000, or 550 to 3000 or 750 to 2500.Succinimide dispersants and their preparation are disclosed, forinstance in U.S. Pat. Nos. 3,172,892, 3,219,666, 3,316,177, 3,340,281,3,351,552, 3,381,022, 3,433,744, 3,444,170, 3,467,668, 3,501,405,3,542,680, 3,576,743, 3,632,511, 4,234,435, Re 26,433, and 6,165,235,7,238,650 and EP Patent Application 0 355 895 A.

The dispersants may also be post-treated by conventional methods by areaction with any of a variety of agents. Among these are boroncompounds (such as boric acid), urea, thiourea, dimercaptothiadiazoles,carbon disulfide, aldehydes, ketones, carboxylic acids such asterephthalic acid, hydrocarbon-substituted succinic anhydrides, maleicanhydride, nitriles, epoxides, and phosphorus compounds. In oneembodiment the post-treated dispersant is borated. In one embodiment thepost-treated dispersant is reacted with dimercaptothiadiazoles. In oneembodiment the post-treated dispersant is reacted with phosphoric orphosphorous acid. In one embodiment the post-treated dispersant isreacted with terephthalic acid and boric acid (as described in U.S.Patent Application US2009/0054278.

When present, the dispersant may be present at 0.01 wt % to 20 wt %, or0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 1 wt % to 6 wt %, or 1to 3 wt % of the lubricating composition.

In one embodiment the lubricating composition disclosed herein furthercomprises an ashless dispersant comprising a succinimide dispersantdifferent from the soot-dispersing additive of the disclosed technology,wherein the succinimide dispersant has a TBN of at least 40 mg KOH/g,and said dispersant is present at 1.2 wt % to 5 wt %, or 1.8 wt % to 4.5wt % of the lubricating composition.

The succinimide dispersant may comprise a polyisobutylene succinimide,wherein the polyisobutylene from which polyisobutylene succinimide isderived has a number average molecular weight of 350 to 5000, or 750 to2500.

In one embodiment the friction modifier may be chosen from long chainfatty acid derivatives of amines, long chain fatty esters, orderivatives of long chain fatty epoxides; fatty imidazolines; aminesalts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyltartrimides; fatty alkyl tartramides; fatty glycolates; and fattyglycolamides. The friction modifier may be present at 0 wt % to 6 wt %,or 0.01 wt % to 4 wt %, or 0.05 wt % to 2 wt %, or 0.1 wt % to 2 wt % ofthe lubricating composition.

As used herein the term “fatty alkyl” or “fatty” in relation to frictionmodifiers means a carbon chain having 10 to 22 carbon atoms, typically astraight carbon chain.

Examples of suitable friction modifiers include long chain fatty acidderivatives of amines, fatty esters, or fatty epoxides; fattyimidazolines such as condensation products of carboxylic acids andpolyalkylene-polyamines; amine salts of alkylphosphoric acids; fattyalkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fattyphosphonates; fatty phosphites; borated phospholipids, borated fattyepoxides; glycerol esters; borated glycerol esters; fatty amines;alkoxylated fatty amines; borated alkoxylated fatty amines; hydroxyl andpolyhydroxy fatty amines including tertiary hydroxy fatty amines;hydroxy alkyl amides; metal salts of fatty acids; metal salts of alkylsalicylates; fatty oxazolines; fatty ethoxylated alcohols; condensationproducts of carboxylic acids and polyalkylene polyamines; or reactionproducts from fatty carboxylic acids with guanidine, aminoguanidine,urea, or thiourea and salts thereof.

Friction modifiers may also encompass materials such as sulfurised fattycompounds and olefins, molybdenum dialkyldithiophosphates, molybdenumdithiocarbamates, sunflower oil or soybean oil monoester of a polyol andan aliphatic carboxylic acid.

In another embodiment the friction modifier may be a long chain fattyacid ester. In another embodiment the long chain fatty acid ester may bea mono-ester and in another embodiment the long chain fatty acid estermay be a triglyceride.

The lubricating composition optionally further includes at least oneantiwear agent. Examples of suitable antiwear agents include titaniumcompounds, tartrates, tartrimides, oil soluble amine salts of phosphoruscompounds, sulfurized olefins, metal dihydrocarbyldithiophosphates (suchas zinc dialkyldithiophosphates), phosphites (such as dibutylphosphite), phosphonates, thiocarbamate-containing compounds, such asthiocarbamate esters, thiocarbamate amides, thiocarbamic ethers,alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl)disulfides. The antiwear agent may in one embodiment include a tartrate,or tartrimide as disclosed in International Publication WO 2006/044411or Canadian Patent CA 1 183 125. The tartrate or tartrimide may containalkyl-ester groups, where the sum of carbon atoms on the alkyl groups isat least 8. The antiwear agent may in one embodiment include a citrateas is disclosed in US Patent Application 20050198894.

Another class of additives includes oil-soluble titanium compounds asdisclosed in U.S. Pat. No. 7,727,943 and US2006/0014651. The oil-solubletitanium compounds may function as antiwear agents, friction modifiers,antioxidants, deposit control additives, or more than one of thesefunctions. In one embodiment the oil soluble titanium compound is atitanium (IV) alkoxide. The titanium alkoxide is formed from amonohydric alcohol, a polyol or mixtures thereof. The monohydricalkoxides may have 2 to 16, or 3 to 10 carbon atoms. In one embodiment,the titanium alkoxide is titanium (IV) isopropoxide. In one embodiment,the titanium alkoxide is titanium (IV) 2 ethylhexoxide. In oneembodiment, the titanium compound comprises the alkoxide of a vicinal1,2-diol or polyol. In one embodiment, the 1,2-vicinal diol comprises afatty acid mono-ester of glycerol, often the fatty acid is oleic acid.

In one embodiment, the oil soluble titanium compound is a titaniumcarboxylate. In a further embodiment the titanium (IV) carboxylate istitanium neodecanoate.

The lubricating composition may in one embodiment further include aphosphorus-containing antiwear agent. Typically thephosphorus-containing antiwear agent may be a zincdialkyldithiophosphate, phosphite, phosphate, phosphonate, and ammoniumphosphate salts, or mixtures thereof. Zinc dialkyldithiophosphates areknown in the art. The antiwear agent may be present at 0 wt % to 3 wt %,or 0.1 wt % to 1.5 wt %, or 0.5 wt % to 0.9 wt % of the lubricatingcomposition.

Extreme Pressure (EP) agents that are soluble in the oil include sulfur-and chlorosulfur-containing EP agents, dimercaptothiadiazole or CS2derivatives of dispersants (typically succinimide dispersants),derivative of chlorinated hydrocarbon EP agents and phosphorus EPagents. Examples of such EP agents include chlorinated wax; sulfurizedolefins (such as sulfurized isobutylene), a hydrocarbyl-substituted2,5-dimercapto-1,3,4-thiadiazole, or oligomers thereof, organic sulfidesand polysulfides such as dibenzyl disulfide, bis-(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid,sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, andsulfurized Diels-Alder adducts; phosphosulfurized hydrocarbons such asthe reaction product of phosphorus sulfide with turpentine or methyloleate; phosphorus esters such as the dihydrocarbon and trihydrocarbonphosphites, e.g., dibutyl phosphite, diheptyl phosphite, dicyclohexylphosphite, pentylphenyl phosphite; dipentylphenyl phosphite, tridecylphosphite, distearyl phosphite and polypropylene substituted phenolphosphite; metal thiocarbamates such as zinc dioctyldithiocarbamate andbarium heptylphenol diacid; amine salts of alkyl and dialkylphosphoricacids or derivatives including, for example, the amine salt of areaction product of a dialkyldithiophosphoric acid with propylene oxideand subsequently followed by a further reaction with P₂O₅; and mixturesthereof (as described in U.S. Pat. No. 3,197,405).

Foam inhibitors that may be useful in the lubricant compositions of thedisclosed technology include polysiloxanes, copolymers of ethyl acrylateand 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiersincluding fluorinated polysiloxanes, trialkyl phosphates, polyethyleneglycols, polyethylene oxides, polypropylene oxides and (ethyleneoxide-propylene oxide) polymers.

Other viscosity modifiers may include a block copolymer comprising (i) avinyl aromatic monomer block and (ii) a conjugated diene olefin monomerblock (such as a hydrogenated styrene-butadiene copolymer or ahydrogenated styrene-isoprene copolymer), a polymethacrylate, ormixtures thereof.

Pour point depressants that may be useful in the lubricant compositionsof the disclosed technology include polyalphaolefins, esters of maleicanhydride-styrene copolymers, poly(meth)acrylates, polyacrylates orpolyacrylamides.

Demulsifiers include trialkyl phosphates, and various polymers andcopolymers of ethylene glycol, ethylene oxide, propylene oxide, ormixtures thereof.

Metal deactivators include derivatives of benzotriazoles (typicallytolyltriazole), 1,2,4-triazoles, benzimidazoles,2-alkyldithiobenzimidazoles or 2-alkyldithiobenzothiazoles. The metaldeactivators may also be described as corrosion inhibitors.

Seal swell agents include sulfolene derivatives Exxon Necton-37™ (FN1380) and Exxon Mineral Seal Oil™ (FN 3200).

An engine lubricant composition in different embodiments may have acomposition as disclosed in the following table:

Embodiments (wt %) Additive A B C Alkylphenol Detergent 0.05 to 10   0.2to 5 0.5 to 2 Corrosion Inhibitor 0.05 to 2    0.1 to 1   0.2 to 0.5Other Overbased Detergent 0 to 9  0.5 to 8   1 to 5 Dispersant ViscosityModifier 0 to 5    0 to 4 0.05 to 2  Dispersant 0 to 12   0 to 8 0.5 to6 Antioxidant 0.1 to 13    0.1 to 10 0.5 to 5 Antiwear Agent 0.1 to 15   0.1 to 10 0.3 to 5 Friction Modifier 0.01 to 6    0.05 to 4  0.1 to 2Viscosity Modifier 0 to 10 0.5 to 8   1 to 6 Any Other Performance 0 to10   0 to 8   0 to 6 Additive Oil of Lubricating Viscosity Balance to100%

INDUSTRIAL APPLICATION

The technology disclosed may include a method of lubricating an internalcombustion engine comprising supplying to the engine a lubricatingcomposition comprising (a) an oil of lubricating viscosity and (b) aphenol-containing detergent comprising at least one unit (a) of analkyl-substituted phenol wherein the alkyl group is derived fromoligomers of an olefin compound containing 3 to 8 carbon atoms, whereinthe polyolefin-derived alkyl group comprises at least 30 mol percent ofan olefin with 4 or more carbon atoms.

The technology disclosed may include a method of lubricating an internalcombustion engine comprising supplying to the engine a lubricatingcomposition comprising (a) an oil of lubricating viscosity, (b) aphenol-containing detergent comprising at least one unit (a) of analkyl-substituted phenol wherein the alkyl group is derived fromoligomers of an olefin compound containing 3 to 8 carbon atoms, whereinthe polyolefin-derived alkyl group comprises at least 30 mol percent ofan olefin with 4 or more carbon atoms, and (c) a zincdialkyldithiophosphate.

The technology disclosed may include a method of lubricating an internalcombustion engine comprising supplying to the engine a lubricatingcomposition comprising (a) an oil of lubricating viscosity, (b) aphenol-containing detergent comprising at least one unit (a) of analkyl-substituted phenol wherein the alkyl group is derived fromoligomers of an olefin compound containing 3 to 8 carbon atoms, whereinthe polyolefin-derived alkyl group comprises at least 30 mol percent ofan olefin with 4 or more carbon atoms, (c) a zincdialkyldithiophosphate, and (d) a polyisobutylene succinimidedispersant.

The internal combustion engine may be a 2-stroke engine, or a 4-strokeengine. Suitable internal combustion engines include marine dieselengines, aviation piston engines, low-load diesel engines, andautomobile and truck engines. The marine diesel engine may be lubricatedwith a marine diesel cylinder lubricant (typically in a 2-strokeengine), a system oil (typically in a 2-stroke engine), or a crankcaselubricant (typically in a 4-stroke engine).

The internal combustion engine may be a 4-stroke engine. The internalcombustion engine may or may not have an Exhaust Gas Recirculationsystem. The internal combustion engine may be fitted with an emissioncontrol system or a turbocharger. Examples of the emission controlsystem include diesel particulate filters (DPF), or systems employingselective catalytic reduction (SCR).

The internal combustion engine may be port fuel injected or directinjection. In one embodiment, the internal combustion engine is agasoline direct injection (GDI) engine.

The lubricating composition may have a total sulfated ash content of 1.2wt % or less. The sulfur content of the lubricating composition may be 1wt % or less, or 0.8 wt % or less, or 0.5 wt % or less, or 0.3 wt % orless. In one embodiment the sulfur content may be in the range of 0.001wt % to 0.5 wt %, or 0.01 wt % to 0.3 wt %. The phosphorus content maybe 0.2 wt % or less, or 0.12 wt % or less, or 0.1 wt % or less, or 0.085wt % or less, or 0.08 wt % or less, or even 0.06 wt % or less, 0.055 wt% or less, or 0.05 wt % or less. In one embodiment the phosphoruscontent may be 0.04 wt % to 0.12 wt %. In one embodiment the phosphoruscontent may be 100 ppm to 1000 ppm, or 200 ppm to 600 ppm. The totalsulfated ash content may be 0.3 wt % to 1.2 wt %, or 0.5 wt % to 1.1 wt% of the lubricating composition. In one embodiment the sulfated ashcontent may be 0.5 wt % to 1.1 wt % of the lubricating composition.

In one embodiment the lubricating composition may be characterized ashaving (i) a sulfur content of 0.5 wt % or less, (ii) a phosphoruscontent of 0.15 wt % or less, and (iii) a sulfated ash content of 0.5 wt% to 1.5 wt % or less.

The lubricating composition may be characterized as having at least oneof (i) a sulfur content of 0.2 wt % to 0.4 wt % or less, (ii) aphosphorus content of 0.08 wt % to 0.15 wt %, and (iii) a sulfated ashcontent of 0.5 wt % to 1.5 wt % or less.

The lubricating composition may be characterized as having a sulfatedash content of 0.5 wt % to 1.2 wt %.

As used herein TBN values are (total base number) measured by themethodology described in D4739 (buffer).

The lubricating composition may be characterized as having a total basenumber (TBN) content of at least 5 mg KOH/g.

The lubricating composition may be characterized as having a total basenumber (TBN) content of 6 to 13 mg KOH/g, or 7 to 12 mg KOH/g. Thelubricant may have a SAE viscosity grade of XW—Y, wherein X may be 0, 5,10, or 15; and Y may be 16, 20, 30, or 40.

The internal combustion engine disclosed herein may have a steel surfaceon a cylinder bore, cylinder block, or piston ring.

The internal combustion engine disclosed herein may be a 2-stroke marinediesel engine, and the disclosed technology may include a method oflubricating a marine diesel cylinder liner of a 2-stroke marine dieselengine.

The internal combustion engine may have a surface of steel, or analuminum alloy, or an aluminum composite. The internal combustion enginemay be an aluminum block engine where the internal surface of thecylinder bores has been thermally coated with iron, such as by a plasmatransferred wire arc (PTWA) thermal spraying process. Thermally coatediron surfaces may be subjected to conditioning to provide ultra-finesurfaces.

The internal combustion engine may have a laden mass (sometimes referredto as gross vehicle weight rating (GVWR)) of over 2,700 kg (or 6,000 USApounds) 2,900 kg, or over 3.00 kg, or over 3,300 kg, or over 3,500 kg,or over 3,700 kg, or over 3,900 kg (or 8,500 USA pounds). Typically theupper limit on the laden mass or GVWR is set by national government andmay be 10,000 kg, or 9,000 kg, or 8,000 kg, or 7,500 kg.

Heavy duty diesel engines are noted to be limited to all motor vehicleswith a “technically permissible maximum laden mass” over 3,500 kg,equipped with compression ignition engines or positive ignition naturalgas (NG) or LPG engines. In contrast, the European Union indicates thatfor new light duty vehicles (passenger cars and light commercialvehicles) included within the scope of ACEA testing section “C” have a“technically permissible maximum laden mass” not exceeding 2610 kg.

There is a distinct difference between passenger car, and heavy dutydiesel engines. The difference in size from over 3,500 kg to not morethan 2610 kg means that engines of both types will experiencesignificantly different operating conditions such as load, oiltemperatures, duty cycle and engine speeds. Heavy duty diesel enginesare designed to maximize torque for hauling payloads at maximum fueleconomy while passenger car diesels are designed for commuting peopleand acceleration at maximum fuel economy. The designed purpose of theengine hauling versus communing results in different hardware designsand resulting stresses imparted to lubricant designed to protect andlubricate the engine. Another distinct design difference is theoperating revolution per minute (RPM) that each engine operates at tohaul versus commute. A heavy duty diesel engine such as a typical 12-13litre truck engine would typically not exceed 2200 rpm while a passengercar engine can go up to 4500 rpm. In one embodiment the internalcombustion engine is a heavy duty diesel compression ignited internalcombustion engine (or a spark assisted compression ignited) internalcombustion engine. Typically the vehicle powered by thecompression-ignition internal combustion engine of the disclosetechnology has a maximum laden mass over 3,500 kg (a heavy duty dieselengine).

The following examples provide illustrations of the disclosedtechnology. These examples are non-exhaustive and are not intended tolimit the scope of the disclosed technology.

EXAMPLES

Detergent examples of the disclosed technology include those prepared bythe following experimental procedures.

Example 1

To a 12 L four-necked round-bottom flask, equipped with a thermowell andnitrogen inlet, with subsurface sparge tube, a Dean-Stark trap,Friedrichs condenser, and a scrubber, is charged 2000 g4-(5-ethyl-7-methylnonan-3-yl)phenol. The4-(5-ethyl-7-methylnonan-3-yl)phenol is heated to 100° C. and 120 ghydrated lime and 45 g ethylene glycol are added. The temperature isincreased to 123° C. and 327 g sulfur is added. The mixture is heated to175° C. and maintained at that temperature for 6 hours, at which time2493 g diluent oil is added and the reaction is allowed to cool.

The material in the reactor is heated to 135° C., and 930 g hydratedlime, 550 g ethylene glycol, 170 g alkylbenzenesulfonic acid, and 700 gdecyl alcohol are added. The mixture is heated to 168° C. and maintainedat that temperature until liquid is no longer readily distilling. Flowof carbon dioxide is begun at 85 L/hr (3 ft³/hr) and continued for 2hours 45 minutes. Volatile materials are removed by stripping at213-218° C. at less than 5300 Pa (40 torr) for 45 minutes. Duringcooling, polyisobutenes-substituted succinic anhydride (300 g) is added.The crude product is filtered through diatomaceous earth. (Actual TBN239; % S 3.23; % Ca 8.76).

Example 2

To a 12 L four-necked round-bottom flask, equipped with a thermowell andnitrogen inlet, with subsurface sparge tube, a Dean-Stark trap,Friedrichs condenser, and a scrubber, is charged 2000 g4-(5,7-diethyl-9-methylundecan-3-yl)phenol. The4-(5,7-diethyl-9-methylundecan-3-yl)phenol is heated to 100° C. and 120g hydrated lime and 45 g ethylene glycol are added. The temperature isincreased to 123° C. and 327 g sulfur is added. The mixture is heated to175° C. and maintained at that temperature for 6 hours, at which time2493 g diluent oil is added and the reaction is allowed to cool.

The material in the reactor is heated to 135° C., and 930 g hydratedlime, 550 g ethylene glycol, 170 g alkylbenzenesulfonic acid, and 700 gdecyl alcohol are added. The mixture is heated to 168° C. and maintainedat that temperature until liquid is no longer readily distilling. Flowof carbon dioxide is begun at 85 L/hr (3 ft³/hr) and continued for 2hours 45 minutes. Volatile materials are removed by stripping at213-218° C. at less than 5300 Pa (40 torr) for 45 minutes. Duringcooling, polyisobutenes-substituted succinic anhydride (300 g) is added.The crude product is filtered through diatomaceous earth. (TheoreticalTBN 245; % S 3.37; % Ca 8.8).

Example 3

To a 12 L four-necked round-bottom flask, equipped with a thermowell andnitrogen inlet, with subsurface sparge tube, a Dean-Stark trap,Friedrichs condenser, and a scrubber, is charged 2429 g4-(5,7-diethyl-9-methylundecan-3-yl)phenol. The4-(5,7-diethyl-9-methylundecan-3-yl)phenol is heated to 100° C. and 120g hydrated lime and 45 g ethylene glycol are added. The temperature isincreased to 123° C. and 327 g sulfur is added. The mixture is heated to175° C. and maintained at that temperature for 6 hours, at which time2063 g diluent oil is added and the reaction is allowed to cool.

The material in the reactor is heated to 135° C., and 930 g hydratedlime, 550 g ethylene glycol, 170 g alkylbenzenesulfonic acid, and 700 gdecyl alcohol are added. The mixture is heated to 168° C. and maintainedat that temperature until liquid is no longer readily distilling. Flowof carbon dioxide is begun at 85 L/hr (3 ft³/hr) and continued for 2hours 45 minutes. Volatile materials are removed by stripping at213-218° C. at less than 5300 Pa (40 torr) for 45 minutes. Duringcooling, polyisobutenes-substituted succinic anhydride (300 g) is added.The crude product is filtered through diatomaceous earth. (TheoreticalTBN 245; % S 3.37; % Ca 8.8).

Example 4

To a 10 L four-necked round-bottom flask, equipped with a thermowell andnitrogen inlet, with subsurface sparge tube, a Dean-Stark trap,Friedrichs condenser, and a scrubber, is charged 2000 g4-(5-ethyl-7-methylnonan-3-yl)phenol. The4-(5-ethyl-7-methylnonan-3-yl)phenol is heated to 100° C. and 177 ghydrated lime and 139 g ethylene glycol are added. The temperature isincreased to 123° C. and 362 g sulfur is added. The mixture is heated to182° C. and maintained at that temperature for 7 hours, at which time862 g diluent oil is added and the reaction is allowed to cool.

The material in the reactor is heated to 135° C., and 139 g hydratedlime, 109 g ethylene glycol, and 257 g decyl alcohol are added. Themixture is heated to 168° C. and maintained at that temperature untilliquid is no longer readily distilling and continued for a further hour.Volatile materials are removed by stripping at 213-218° C. at less than5300 Pa (40 torr) for 45 minutes. The crude product is filtered throughdiatomaceous earth. (Theoretical TBN 145; % S 4.7; % Ca 5.3).

Example 5

To a 10 L four-necked round-bottom flask, equipped with a thermowell andnitrogen inlet, with subsurface sparge tube, a Dean-Stark trap,Friedrichs condenser, and a scrubber, is charged 2000 g4-(5,7-diethyl-9-methylundecan-3-yl)phenol. The4-(5,7-diethyl-9-methylundecan-3-yl)phenol is heated to 100° C. and 177g hydrated lime and 139 g ethylene glycol are added. The temperature isincreased to 123° C. and 362 g sulfur is added. The mixture is heated to182° C. and maintained at that temperature for 7 hours, at which time862 g diluent oil is added and the reaction is allowed to cool.

The material in the reactor is heated to 135° C., and 139 g hydratedlime, 109 g ethylene glycol, and 257 g decyl alcohol are added. Themixture is heated to 168° C. and maintained at that temperature untilliquid is no longer readily distilling and continued for a further hour.Volatile materials are removed by stripping at 213-218° C. at less than5300 Pa (40 torr) for 45 minutes. The crude product is filtered throughdiatomaceous earth. (Theoretical TBN 145; % S 4.7; % Ca 5.3).

Example 6

To a 10 L four-necked round-bottom flask, equipped with a thermowell andnitrogen inlet, with subsurface sparge tube, a Dean-Stark trap,Friedrichs condenser, and a scrubber, is charged 2429 g4-(5,7-diethyl-9-methylundecan-3-yl)phenol. The4-(5,7-diethyl-9-methylundecan-3-yl)phenol is heated to 100° C. and 177g hydrated lime and 139 g ethylene glycol are added. The temperature isincreased to 123° C. and 362 g sulfur is added. The mixture is heated to182° C. and maintained at that temperature for 7 hours, at which time433 g diluent oil is added and the reaction is allowed to cool.

The material in the reactor is heated to 135° C., and 139 g hydratedlime, 109 g ethylene glycol, and 257 g decyl alcohol are added. Themixture is heated to 168° C. and maintained at that temperature untilliquid is no longer readily distilling and continued for a further hour.Volatile materials are removed by stripping at 213-218° C. at less than5300 Pa (40 torr) for 45 minutes. The crude product is filtered throughdiatomaceous earth. (Theoretical TBN 145; % S 4.7; % Ca 5.3).

Detergent examples of the disclosed technology also includesulfur-coupled phenates, methylene-coupled phenates (saligenin),salixrate, and salicylate. Examples of alkylphenol susbstrates of thedisclosed technology are summarized in Table 1 below:

TABLE 1 Alkylphenol Substrates Phenol Type No. Repeat (Structure)¹ AlkylGroup (R)² Bridge (X) Units (n)³ AP1 S-Phenate (I) Tetrapropenyl (TP)Sulfur (S) 2 AP2 Salicylate TP — — AP3 S-Phenate (I) Tetrabutenyl (TB)Sulfur (S) 3 AP4 Saligenin (IV) TB Methylene 3 (—CH₂—) AP5 Salixarate(V) TB Methylene 3 (—CH₂—) AP6 Salicylate (VI) TB — — AP7 Salicylate(VI) Pentabutenyl (PB) — — AP8 S-Phenate (I) PB Sulfur (S) 2 AP9S-Phenate (I) Tributenyl (TrB) Sulfur (S) 2 ¹The number in parentheses () refers to structural formula types in the specification ²From thestructural formulas (R) refers to the primary hydrocarbyl group found inthe para-position to the phenol moiety ³From the structural formulas (n)refers to an approximation of the phenolic units in addition to basephenol unit

Detergents, both neutral and overbased, may be prepared with thesubstrates summarized above. Detergents of the disclosed technology aresummarized in Table 2 below:

TABLE 2 Alkylphenol-containing Detergents¹ Theoretical Phenol Counterion% Metal Metal Ratio² CEX1 AP1 Calcium 15 3.5 CEX2 AP1 Calcium 7.1 1.1CEX3 AP2 Calcium 10 2.5 EX4 AP3 Calcium 14 3.5 EX5 AP3 Calcium 7 1.1 EX6AP8 Calcium 14 3.5 EX7 AP4 Magnesium 3 0.8 EX8 AP7 Calcium 9.6 2.5 EX9AP7 Calcium 18 6 EX10 AP8 Calcium 9 3 EX11 AP7 Tetrabutyl 0 1.0 ammonium(TBA) EX12 AP9 Calcium 8.76³ 3.7 ¹All analyticals are on an oil-freebasis ²Ratio of equivalents of counterion to equivalents of phenolsubstrate; metal ratio in excess of 1.2 is deemed overbased ³Measuredvalue

The Total Base Number (TBN) may be determined using the methodology ofASTM D2896.

A series of engine lubricants in Group III base oil of lubricatingviscosity are prepared containing the additives described above as wellas conventional additives including polymeric viscosity modifier,ashless succinimide dispersant, overbased detergents different from thatof the disclosed technology, antioxidants (combination of phenolicester, diarylamine, and sulfurized olefin), zinc dialkyldithiophosphate(ZDDP), as well as other performance additives as follows (Table 3):

TABLE 3 Lubricant Compositions¹ OIL1 OIL2 OIL3 OIL4 OIL5 OIL6 OIL7 BaseOil Balance to 100% CEX1 0.4 0.6 CEX2 0.33 0.1 CEX3 1.0 EX4 0.4 0.6 EX50.33 0.1 EX8 1.0 EX11 1.8 Sulfonate² 1.0 0.5 1.0 1.0 1.0 0.5 0.3 ZDDP³1.1 1.1 1.1 1.1 1.1 1.1 0.5 Antioxidant⁴ 0.44 0.44 0.44 0.44 0.44 0.44Dispersant⁵ 3.1 3.1 3.1 3.1 3.1 3.1 Viscosity 1.0 1.0 1.0 1.0 1.0 1.0Modifier⁶ Additional 0.34 0.34 0.34 0.34 0.34 0.34 additives⁷ ¹All treatrates on an oil-free basis ²Overbased calcium sulfonate detergents³Secondary ZDDP derived from mixture of C3 and C6 alcohols ⁴Sulfurizedolefin ⁵Succinimide dispersant derived from succinated polyisobutylene(Mn 2000) ⁶Ethylene-propylene copolymer with Mn of 90,000 ⁷Additionaladditives include surfactant, corrosion inhibitor, anti-foam agents,friction modifiers, and pourpoint depressants

TABLE 4 Lubricant Compositions OIL8 OIL9 Base Oil Balance to 100% GroupIII Base Oil 72 72 PAO-4 28 28 CEX1 0.98 EX12 0.98 Sulfonate Detergent²0.06 0.06 ZDDP³ 0.79 0.79 Antioxidant⁴ 3.6 3.6 Dispersant⁵ 6.2 6.2Viscosity Modifier⁶ 1.1 1.1 Additional additives⁷ 0.3 0.3 ¹All treatrates on an oil-free basis ²Overbased calcium sulfonate detergent (700TBN) ³Secondary ZDDP derived from mixture of C3 and C6 alcohols ⁴Mixtureof hindered phenol, alkylated diarylamine, and sulfurized olefin⁵Succinimide dispersant derived from high vinylidene polyisobutylene⁶Styrene-butadiene block copolymer ⁷Additional additives includesurfactant, corrosion inhibitor, anti-foam agents, friction modifiers,and pourpoint depressants

The lubricants may be evaluated for cleanliness, i.e. the ability toprevent or reduce deposit formation; sludge handling; soot handling;antioxidancy; and wear reduction.

Anti-wear performance is measured in a programmed temperature highfrequency reciprocating rig (HFRR) available from PCS Instruments. HFRRconditions for the evaluations are 200 g load, 75 minute duration, 1000micrometer stroke, 20 hertz frequency, and temperature profile of 15minutes at 40° C. followed by an increase in temperature to 160° C. at arate of 2° C. per minute. Wear scar in micrometers and film formation aspercent film thickness are then measured with lower wear scar values andhigher film formation values indicating improved wear performance.

Deposit control is measured by the Komatsu Hot Tube (KHT) test, whichemploys heated glass tubes through which sample lubricant is pumped,approximately 5 mL total sample, typically at 0.31 mL/hour for anextended period of time, such as 16 hours, with an air flow of 10mL/minute. The glass tube is rated at the end of test for deposits on ascale of 0 (very heavy varnish) to 10 (no varnish).

In the Panel Coker deposit test, the sample, at 105° C., is splashed for4 hours on an aluminum panel maintained at 325° C. The aluminum platesare analyzed using image analysis techniques to obtain a universalrating. The rating score is based on “100” being a clean plate and “0”being a plate wholly covered in deposit.

Oxidation control is evaluated utilizing pressure differential scanningcalorimtery (PDSC) which determines oxidation induction time (OIT) forlubricating compositions. This is a standard test procedure in thelubricating oil industry, based on CEC L-85 T-99. In this testing thelubricating composition is heated to an elevated temperature, typicallyabout 25° C. below the average decomposition temperature for the samplebeing tested (in this case 215° C. at 690 kPa), and the time to when thecomposition begins to decompose is measured. The longer the test time,reported in minutes, the better the oxidative stability of thecomposition and the additives present within it.

TABLE 5 Performance Testing OIL8 OIL9 ASTM D6335 (TEOST 33C) RodDeposits (mg) 18.3 18.4 Filter Deposits (mg) 12.3 13.2 Total Deposits(mg) 30.6 31.6 ASTM D7097B (MHT TEOST) Net deposits-depositor rod (mg)8.8 5.9 Filter net deposits (mg) 0 0.7 Total Deposits (mg) 8.8 6.6 CECL-85-T-99 (PDSC) Oxidation induction time (min) 88.8 129 Panel CokerUniversal Rating (%) 72 75

As the data illustrates, replacement of the tetrapropenylphenol-basedphenate detergent (OIL8) with the tributenylphenol-based phenate (OIL9)results in equivalent or better performance in deposit control andsignificant improvement in oxidative stability (OIT).

It is known that some of the materials described above may interact inthe final formulation, so that the components of the final formulationmay be different from those that are initially added. The productsformed thereby, including the products formed upon employing lubricantcomposition of the present invention in its intended use, may not besusceptible of easy description. Nevertheless, all such modificationsand reaction products are included within the scope of the presentinvention; the present invention encompasses lubricant compositionprepared by admixing the components described above.

Each of the documents referred to above is incorporated herein byreference. Except in the Examples, or where otherwise explicitlyindicated, all numerical quantities in this description specifyingamounts of materials, reaction conditions, molecular weights, number ofcarbon atoms, and the like, are to be understood as modified by the word“about”. Unless otherwise indicated, each chemical or compositionreferred to herein should be interpreted as being a commercial gradematerial which may contain the isomers, by-products, derivatives, andother such materials which are normally understood to be present in thecommercial grade. However, the amount of each chemical component ispresented exclusive of any solvent or diluent oil, which may becustomarily present in the commercial material, unless otherwiseindicated. It is to be understood that the upper and lower amount,range, and ratio limits set forth herein may be independently combined.Similarly, the ranges and amounts for each element of the invention maybe used together with ranges or amounts for any of the other elements.

While the invention has been explained in relation to its preferredembodiments, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thespecification. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modifications as fall withinthe scope of the appended claims.

What is claimed:
 1. An alkylphenol-containing detergent comprising atleast one unit (a) of an alkyl-substituted phenol wherein the alkylgroup is derived from oligomers of an olefin compound containing 3 to 8carbon atoms, wherein the polyolefin-derived alkyl group comprises atleast 30 mol percent of an olefin with 4 or more carbon atoms.
 2. Analkylphenol-containing detergent of claim 1, where the phenol-containingdetergent is a sulfur-bridged phenate detergent, a sulfur-freealkylene-bridged phenate detergent, a salicylate detergent, or mixturesthereof.
 3. An alkylphenol-containing detergent of claim 2, where thedetergent comprises one or more alkali metals, one or more alkalineearth metals, or mixtures thereof.
 4. An alkylphenol-containingdetergent of claim 3, where the detergent is overbased.
 5. Analkylphenol-containing detergent of claim 4, where the overbaseddetergent has a metal ratio of at least 1.5, at least 5, or at least 7.6. An alkylphenol-containing detergent of claim 1, where the alkyl groupcomprises oligomers of n-butene, where the alkyl group is a hydrocarbylgroup of 12 to 48 carbon atoms.
 7. An alkylphenol-containing detergentof claim 1, wherein the detergent is an overbased sulfur-coupled phenatedetergent with a metal ratio of at least 1.5.
 8. Analkylphenol-containing detergent of claim 1, wherein the alkylphenol isa sulfur-bridged phenate represented by the structure

wherein each R is an aliphatic hydrocarbyl group derived from oligomersof n-butene, higher alphaolefins, or mixtures thereof, that contains 8to 48 carbon atoms; and n=0 to 8, or 1 to 6, or 1 to 4, or 2 to
 4. 9. Analkylphenol-containing detergent of claim 1, wherein the detergent is aneutral or overbased salt of alkylsalicylic acid.
 10. Analkylphenol-containing detergent of claim 1, wherein the alkylphenol isan alkylsalicylate represented by the structure

where R is an aliphatic hydrocarbyl group derived from oligomers ofn-butene, higher alphaolefins, or mixtures thereof, and wherein thehydrocarbyl group contains 8 to 48 carbon atoms
 11. A lubricatingcomposition comprising (a) an oil of lubricating viscosity and (b) Aphenol-containing detergent comprising at least one unit (a) of analkyl-substituted phenol wherein the alkyl group is derived fromoligomers of an olefin compound containing 3 to 8 carbon atoms, whereinthe polyolefin-derived alkyl group comprises at least 30 mol percent ofan olefin with 4 or more carbon atoms.
 12. A lubricating composition ofclaim 11, wherein the composition is substantially free of analkylphenol-containing detergent wherein the alkylphenol is derived fromoligomers of propene.
 13. The lubricating composition of claim 11,further comprising additional additives selected from an overbaseddetergent different from alkylphenol-containing detergent of anypreceding claims 1 to 11, an ashless dispersant, a phosphorus-containinganti-wear agent, an antioxidant, a corrosion inhibitor, a viscosityindex improver, or combinations thereof.
 14. The lubricating compositionof claim 13, further comprising 0.01 to 3 weight percent of a calciumoverbased alkylbenzene sulfonate detergent.
 15. The lubricatingcomposition of claim 13, further comprising 0.01 to 0.15 weight percentof a phosphorus containing anti-wear agent.
 16. A method of lubricatingan internal combustion engine comprising supplying to the engine alubricating composition comprising (a) an oil of lubricating viscosityand (b) A phenol-containing detergent comprising at least one unit (a)of an alkyl-substituted phenol wherein the alkyl group is derived fromoligomers of an olefin compound containing 3 to 8 carbon atoms, whereinthe polyolefin-derived alkyl group comprises at least 30 mol percent ofan olefin with 4 or more carbon atoms.
 17. The method of claim 17,wherein the lubricating composition further comprises a zincdialkyldithiophosphate.
 18. The method of claim 17, wherein thelubricating composition further comprises polyisobutylene succinimidedispersant.
 19. The method of claim 17, wherein the lubricatingcomposition further comprises a zinc dialkyldithiophosphate, and (d) apolyisobutylene succinimide dispersant.
 20. The method of claim 17,wherein the internal combustion engine is a heavy duty dieselcompression ignited internal combustion engine or a spark assistedcompression ignited internal combustion engine.